CN108054019A - Laminated construction NiCo2S4@NixCo(1-x)(OH)2The preparation method and application of composite material - Google Patents
Laminated construction NiCo2S4@NixCo(1-x)(OH)2The preparation method and application of composite material Download PDFInfo
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- CN108054019A CN108054019A CN201710619321.3A CN201710619321A CN108054019A CN 108054019 A CN108054019 A CN 108054019A CN 201710619321 A CN201710619321 A CN 201710619321A CN 108054019 A CN108054019 A CN 108054019A
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- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000010276 construction Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910006176 NixCo Inorganic materials 0.000 title description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 37
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- 239000006260 foam Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 6
- 238000004070 electrodeposition Methods 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004202 carbamide Substances 0.000 claims abstract description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002060 nanoflake Substances 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 238000004062 sedimentation Methods 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 15
- 239000003990 capacitor Substances 0.000 abstract description 7
- 239000011149 active material Substances 0.000 abstract description 4
- 238000003487 electrochemical reaction Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KTPIHRZQGZDLSN-UHFFFAOYSA-N cobalt;nitric acid Chemical compound [Co].O[N+]([O-])=O KTPIHRZQGZDLSN-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 3
- 235000013495 cobalt Nutrition 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- -1 transition metal (hydrogen) oxide Chemical class 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- DHPNXAFERMWNAB-UHFFFAOYSA-L [Ni](O)O.[O-2].[O-2].[Mn+4] Chemical compound [Ni](O)O.[O-2].[O-2].[Mn+4] DHPNXAFERMWNAB-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011165 3D composite Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 241000257465 Echinoidea Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910016719 Ni0.5Co0.5(OH)2 Inorganic materials 0.000 description 1
- 229910017062 Ni0.67Co0.33(OH)2 Inorganic materials 0.000 description 1
- 241000209094 Oryza Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000224 chemical solution deposition Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 1
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 description 1
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a kind of laminated construction NiCo2S4@NixCo(1‑x)(OH)2The preparation method and application of composite material, comprises the following steps：Nickel foam is placed in and is prepared with deionized water and absolute ethyl alcohol in the mixed solution of nickel nitrate, cobalt nitrate and urea, hydro-thermal reaction obtains foamed nickel supported NiCo in reaction kettle2S4Presoma；It in sodium sulfide solution is vulcanized, spongy NiCo is made2S4Nano flake；It is made again with galvanostatic method electro-deposition and is grown on NiCo securely in a manner of setting2S4The Ni that outer layer, size are interspersedxCo(1‑x)(OH)2Nanometer sheet.Composite material prepared by the present invention has unique, novel 3-D stacks structure, there are a large amount of holes between nanometer sheet, contact of the active material with electrolyte can be effectively increased and participate in electrochemical reaction, be a kind of electrode material for super capacitor with very high specific capacitance/area specific capacitance.
Description
Technical field
The present invention relates to laminated construction NiCo2S4@NixCo(1-x)(OH)2The preparation method and application of composite material, belongs to and receives
Nano composite material synthesizes and supercapacitor technologies field.
Background technology
With economic rapid development, energy shortage and environmental degradation problem highlight, and development environment is friendly, renewable, utilization
The high novel energy conversion of rate is extremely urgent with storage device.As a kind of novel energy storage apparatus, ultracapacitor, which has, to charge
The advantages that speed is fast, power density is high, service life is long, environmentally protective, in electric vehicle, mobile electronic equipment, guided missile dress
The hybrid powers such as standby, space flight and aviation field has wide application prospect.However, the energy density of capacitor is relatively low at present, much
Less than lithium battery, and usually with high specific area carbon and expensive RuO2For electrode material, it is impossible to meet demand.
Ultracapacitor is divided into double layer capacitor and pseudocapacitors according to energy storage mechnism difference, before the latter's performance is better than
Person.At present, the electrode material of pseudocapacitors is mainly transition metal (hydrogen) oxide, transient metal sulfide and conducting polymer
Object, especially with NiCo2O4、NiCo2S4For the bimetallic oxide and sulfide of representative, due to having than its single metal oxides
Electric conductivity better with sulfide and more superior chemical property and be subject to hot handful.
On the preparation of transition metal (hydrogen) oxide, sulfide and its composite electrode material and its in ultracapacitor
In application it has been reported that being received as Singapore Zhe Tang et al. prepare gauze-like on the carbon nanotubes using chemical bath deposition method
Rice Ni (OH)2Composite material, area specific capacitance are 16F/cm2(Zhe Tang,Chun-hua Tang,Hao Gong,
Adv.Funct.Mater.,2012,22,1272-1278).Patent CN103553151B, a kind of " electrode material for super capacitor
The preparation method of nickel oxide " using nickel acetate tetrahydrate as raw material, at 180 DEG C after hydro-thermal method reaction 16h calcines, is made more again
The flower-like structure nickel oxide in hole, the specific capacitance in 50mV/s are 912F/g.Liang Huang et al. are existed using potentiostatic method
NiCo2O4Nickel cobalt double hydroxide nano piece is prepared on nano wire/carbon fiber paper, highest area specific capacitance is 1.64F/cm2
(Liang Huang,Dongchang Chen,Yong Ding,Shi Feng,Zhong Lin Wang,and Meilin Liu,
Nano Lett.,2013,13,3135-3139).Patent CN103065806B, " sodium ion embedded type manganese dioxide nano-plates electricity
Pole and its preparation method and application " carries out electro-deposition using chronoptentiometry, sodium ion embedded type manganese dioxide nano-plates is made
Electrode, electrode capacity are up to 1F/cm2.Patent CN102709058B " prepares ultracapacitor manganese dioxide-nickel hydroxide
Specific capacitance of the manganese dioxide-nickel hydroxide composite electrode material that the method for combination electrode material " is invented in 5A/g is reachable
2334F/g.Patent CN104465117A, " prepared by a kind of cobalt acid zinc@manganese dioxide nucleocapsid heterogeneous structural nano pipes array material
Specifically capacitance is the cobalt acid zinc@manganese dioxide nucleocapsid heterogeneous structural nano pipes array material maximum that method and its application " are invented
2458F/g.Haichao Chen et al. prepare sea urchin shape Ni nanoparticle Co2S4, I-V test displays, compared with NiCo2O4With more
High electric conductivity (Haichao Chen, Jianjun Jiang, Li Zhang, Houzhao Wan, Tong Qi, Dandan
Xia, Nanoscale, 2013,5,8879-8883), highest specific capacitance is 1149F/g, 5000 cycles, and capacity retention is
91.4%.Patent CN104795245A, a kind of " wire nickel cobalt oxide@nickel cobalts sulfide heterojunction structure composite material preparation side
Method and purposes ", the wire nickel cobalt oxide@nickel cobalt sulfide heterojunction structure composite electrodes invented are in 5mA/cm2When
The specific capacitance of maximum be 2424F/g, area specific capacitance is 4.8F/cm2.Recently, J.Zhang et al. reports are using potentiostatic method
NiCo is prepared on carbon cloth2S4Nanotube/Ni (OH)2Nanometer sheet nucleocapsid electrode material, in 1mA/cm2When highest ratio
Capacitance is 2700F/g (J.Zhang, H.Gao, M.Y.Zhang, Q.Yang, H.X.Chuo, Applied Surface
Science,2015,349,870-875).In conclusion bimetallic sulfide is expected to become capacitance with bimetallic (hydrogen) oxide
The ideal electrode material of device.
Although the preparation of transition metal (hydrogen) oxide, sulfide and its composite material in recent years and its as super capacitor
The research of device electrode achieves gratifying achievement, but prepared electrode material in terms of chemical property also there are some not
Foot.Such as：The specific capacitance of single transition metal oxide is not high；The composite material of transition metal oxide, sulfide and hydroxide
It is mostly the nucleocapsid of nano wire@nanometer sheets or nanometer sheet@nano wires, is greatly improved although the specific capacitance of electrode has,
It is since load capacity is relatively fewer, area specific capacitance is relatively low.Therefore, exploitation one kind is of low cost, load capacity is high has simultaneously
The electrode material for super capacitor of high specific capacitance/area specific capacitance and excellent cycle stability has important research and should
With value.
The content of the invention
For existing electrode material in terms of chemical property existing deficiency, the present invention provides a kind of laminated construction
NiCo2S4@NixCo(1-x)(OH)2The preparation method and application of composite material, composite material obtained have high specific capacitance/face
Product specific capacitance and excellent cyclical stability, can be directly as the electrode of ultracapacitor.Preparation comprises the following steps：
(1) nickel foam is immersed in the oxide that 15min in the hydrochloric acid solution of 3mol/L removes surface, is then being gone successively
It is after being cleaned by ultrasonic in ionized water and absolute ethyl alcohol and dry, clean nickel foam is obtained, is placed it in after weighing standby in reaction kettle
With；
(2) it is 1 with volume ratio：It is 0.017mol/ that 1 deionized water prepares nitric acid nickel concentration with absolute ethyl alcohol mixed solvent
The concentration ratio of L, 2 times of nickel nitrates of nitric acid cobalt concentration, urea and nitrate is 5:1 mixed solution, and be transferred to and fill clean bubble
In the reaction kettle of foam nickel, 6h is reacted at 120 DEG C, after being then cleaned by ultrasonic reaction in deionized water and absolute ethyl alcohol successively
Nickel foam and drying obtain foamed nickel supported NiCo2S4Precursor A；
(3) sodium sulfide solution and A that concentration is 0.067mol/L are placed in reaction kettle, 12h is reacted at 90 DEG C, and is pressed
Step (2) is described to be cleaned and is dried, and obtains foamed nickel supported NiCo2S4, it is denoted as B；
(4) it is (0~2) to prepare nickel nitrate with cobalt nitrate concentration ratio:1, nitrate total concentration is that the mixing of 0.1mol/L is molten
Liquid is as electrolyte C；
(5) using B as working electrode, platinum filament is to electrode, and saturated calomel electrode is reference electrode, controls the current density to be
20mA/cm2, the constant current electro-deposition 10min in electrolyte C, then by step (2) cleaning and dry working electrode, system
Obtain foamed nickel supported laminated construction NiCo2S4@NixCo(1-x)(OH)2Composite material.
Present device is simple, and raw material sources are extensive, and manufacturing cost is low, prepares the Ni of product outer layerxCo(1-x)(OH)2It receives
Rice piece is interspersed, and is grown on spongy NiCo securely in a manner of setting2S4Outer layer forms unique, novel laminated construction
NiCo2S4@NixCo(1-x)(OH)2Three-dimensional composite material.The nanometer sheet of the electrode material has between large specific surface area and piece and piece
A large amount of holes, can not only effectively increase the contact area of active material and electrolyte, and be conducive to electrolyte in electricity
It rapidly penetrates into and oozes out in chemical reaction process, active material load capacity is high in addition, makes it have very high specific capacitance/area
Specific capacitance and good cyclical stability, can be widely applied to new-energy automobile, track traffic, lifting device and military equipment etc.
The field of hybrid power energy demand.
Description of the drawings
Fig. 1 is the foamed nickel supported NiCo prepared by embodiment 12S4Stereoscan photograph.
Fig. 2 is the foamed nickel supported laminated construction NiCo prepared by embodiment 12S4@Ni0.33Co0.67(OH)2Composite material
Stereoscan photograph.
Fig. 3 is the foamed nickel supported laminated construction NiCo prepared by embodiment 12S4@Ni0.33Co0.67(OH)2Composite material
Electrochemical property test figure：(a) cyclic voltammetry curve under different scanning speed；(b) charge and discharge under different current densities are bent
Line；(c) specific capacitance/area specific capacitance curve under different current densities；(d) current density is 40mA/cm2When pass through 500 times
The area specific capacitance variation diagram for cycling, illustration are 4 charging and discharging curves cycled of beginning.
Fig. 4 is the foamed nickel supported laminated construction NiCo prepared by embodiment 2 to example 42S4@NixCo(1-x)(OH)2Composite wood
Material is 30mA/cm in current density2Under charging and discharging curve figure.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
(1) nickel foam is immersed in 15min in the hydrochloric acid solution of 3mol/L, to remove oxide on surface, then to go successively
Respectively it is cleaned by ultrasonic in ionized water and absolute ethyl alcohol 3 times, dry 1h, obtains the nickel foam of clean dried, after weighing at 60 DEG C
It places it in spare in reaction kettle；
(2) it is 1 with volume ratio：1 deionized water and absolute ethyl alcohol mixed solvent preparation nickel nitrate, cobalt nitrate and urea are dense
Degree is respectively the mixed solution 60mL of 0.017mol/L, 0.034mol/L and 0.255mol/L, and is transferred to and fills clean foam
In the reaction kettle of nickel, cooled to room temperature after hydro-thermal reaction 6h is carried out at 120 DEG C, successively in deionized water and absolute ethyl alcohol
Each 3 times of nickel foam after middle ultrasonic cleaning reaction, dry 12h, obtains foamed nickel supported NiCo at 60 DEG C2S4Precursor A；
(3) take 60mL concentration foamed nickel supported for 0.067mol/L sodium sulfide solutions and prepared by step (2)
NiCo2S4Precursor A reacts cooled to room temperature after 12h in reaction kettle at 90 DEG C, then successively in deionized water and
Each 3 times of nickel foam in absolute ethyl alcohol after ultrasonic cleaning reaction, dry 12h, obtains foamed nickel supported NiCo at 60 DEG C2S4,
B is denoted as, active material load capacity is 2.6mg/cm2；
(4) preparation nickel nitrate and nitric acid cobalt concentration are respectively that the mixed solution 35mL of 0.033mol/L and 0.067mol/L makees
For electrolyte C；
(5) using the B prepared by step (3) as working electrode, platinum filament is to electrode, and saturated calomel electrode is reference electrode,
It is 20mA/cm to control current density2, it is then described clear by step (2) using galvanostatic method electro-deposition 10min in electrolyte C
Working electrode is washed and dried, foamed nickel supported laminated construction NiCo is made2S4@Ni0.33Co0.67(OH)2Composite material, active matter
Matter total load amount is 5.9mg/cm2。
Prepared Ni nanoparticle Co2S4Stereoscan photograph see Fig. 1.As can be seen from Figure 1, NiCo2S4Nano flake is with phase
The form uniform fold to connect is in foam nickel surface, in the spongy pattern with a large amount of tiny holes.
Prepared laminated construction NiCo2S4@Ni0.33Co0.67(OH)2The stereoscan photograph of composite material is shown in Fig. 2.From figure
2 can be seen that, Ni0.33Co0.67(OH)2For the nanometer sheet that size differs greatly, sheet has well-regulated hexagon geometry, small
Piece is interspersed around sheet, there is a large amount of holes between piece；Ni0.33Co0.67(OH)2Nanometer sheet is grown securely in a manner of erectting
In Ni nanoparticle Co2S4Outer layer forms unique, novel 3-D stacks structure.
With prepared foamed nickel supported laminated construction NiCo2S4@Ni0.33Co0.67(OH)2Composite material is working electrode,
Platinum filament is to electrode, and saturated calomel electrode builds three-electrode system for reference electrode, carries out electrochemical property test, including Xun Huan
Volt-ampere test and constant current charge-discharge test.Electrolyte is the KOH solution of 6mol/L, and charging/discharging voltage is 0~0.4V, and electric current is close
It spends for 5~70mA/cm2, the current density of cyclical stability test is 40mA/cm2。
Prepared laminated construction NiCo2S4@Ni0.33Co0.67(OH)2The result is shown in figures for the electrochemical property test of composite material
3.Wherein Fig. 3 (a) is the cyclic voltammetry curve under different scanning speed, be can be seen that by Fig. 3 (a), every curve has a pair of of oxygen
Change reduction peak, show the fake capacitance characteristic of electrode.Fig. 3 (b) is the constant current charge-discharge curve under different current densities, by Fig. 3 (b)
It can be seen that, be 5mA/cm in current density2When, the most long charge and discharge time reaches 2915s, illustrates that electrode has higher capacity.
All curves have voltage platform, have further demonstrated that the fake capacitance characteristic of electrode.Fig. 3 (c) is the ratio under different current densities
Capacitance/area specific capacitance curve, can be seen that, NiCo by Fig. 3 (c)2S4@Ni0.33Co0.67(OH)2Electrode is 5mA/ in current density
cm2、30mA/cm2And 70mA/cm2When, specific capacitance and area specific capacitance are respectively 3192F/g and 19.02F/cm2、2109F/g
And 12.57F/cm2, 1618F/g and 9.64F/cm2.Fig. 3 (d) is that current density is 40mA/cm2When by 500 times cycle face
Product specific capacitance variation, product specific capacitance conservation rate is 100.2% to 500 Xun Huans below.As it can be seen that foamed nickel supported laminated construction
NiCo2S4@Ni0.33Co0.67(OH)2Composite material has very high specific capacitance/area specific capacitance, high rate performance and cyclical stability,
With the potentiality applied to next-generation electrode material for super capacitor.
Embodiment 2
Cobalt nitrate solution using concentration as 0.1mol/L is electrolyte D, controls other conditions and the same embodiment of operating method
1, foamed nickel supported laminated construction NiCo is made2S4@Co(OH)2Composite material, and carry out constant current charge-discharge test.
Embodiment 3
Using nickel nitrate and nitric acid cobalt concentration be 0.05mol/L mixed solution as electrolyte D, control other conditions and behaviour
Make method with embodiment 1, foamed nickel supported laminated construction NiCo is made2S4@Ni0.5Co0.5(OH)2Composite material, and carry out permanent electricity
Flow charge-discharge test.
Embodiment 4
Using nickel nitrate and nitric acid cobalt concentration be respectively 0.067mol/L and 0.033mol/L mixed solution as electrolyte D,
Control other conditions and operating method that foamed nickel supported laminated construction NiCo is made with embodiment 12S4@Ni0.67Co0.33(OH)2It is multiple
Condensation material, and carry out constant current charge-discharge test.
Foamed nickel supported NiCo prepared by embodiment 2 to example 42S4And laminated construction NiCo2S4@NixCo(1-x)(OH)2It is multiple
Condensation material is 30mA/cm in current density2Under charging and discharging curve see Fig. 4.It can be seen from the figure that the laminated construction prepared is answered
Condensation material is than individual layer NiCo2S4The discharge time of nano material is long, illustrates that capacitance is also higher.When x is respectively 0,0.5,0.67,
Each electrode specific capacitance and area specific capacitance of composite material with laminated construction are respectively 848F/g and 5.51F/cm2,
1050F/g and 5.91F/cm2, 1574F/g and 8.66F/cm2, show prepared composite material in high current density 30mA/cm2
It is lower that there is higher capacity, it can be directly as the electrode material of ultracapacitor.
Claims (4)
1. laminated construction NiCo2S4@NixCo(1-x)(OH)2The preparation method and application of composite material, it is characterised in that prepare by such as
Lower step is completed：
(1) nickel foam and drying are cleaned；
(2) using deionized water and absolute ethyl alcohol as mixed solvent, nickel nitrate, cobalt nitrate and urea mixed solution is prepared, and is transferred to
It fills and hydro-thermal reaction is carried out in the reaction kettle of clean nickel foam, be then cleaned by ultrasonic successively in deionized water and absolute ethyl alcohol anti-
Nickel foam and drying after answering, obtain foamed nickel supported NiCo2S4Precursor A；
(3) sodium sulfide solution and A are placed in reaction kettle and carry out hydro-thermal reaction, and cleaned and dried by step (2) is described,
Obtain foamed nickel supported NiCo2S4, it is denoted as B；
(4) nickel nitrate and cobalt nitrate are dissolved in deionized water, electrolyte C is made；
(5) using B as working electrode, platinum filament is to electrode, and saturated calomel electrode is reference electrode, using permanent electricity in electrolyte C
Stream method carries out electro-deposition, then by step (2) cleaning and dry working electrode to get foamed nickel supported laminated construction
NiCo2S4@NixCo(1-x)(OH)2Composite material.
2. laminated construction NiCo according to claim 12S4@NixCo(1-x)(OH)2The preparation method of composite material and should
With, which is characterized in that the nitrate total concentration of the electrolyte obtained by step (4) is 0.1mol/L, wherein nickel nitrate and nitric acid
The concentration ratio of cobalt is (0~2):1.
3. laminated construction NiCo according to claim 12S4@NixCo(1-x)(OH)2The preparation method of composite material and should
With, which is characterized in that the current density of galvanostatic method electro-deposition is 20mA/cm in step (5)2, sedimentation time 10min.
4. laminated construction NiCo according to claim 12S4@NixCo(1-x)(OH)2The preparation method of composite material and should
With, which is characterized in that prepared composite material is with foamed nickel supported spongy NiCo2S4Nano flake is skeleton, NixCo(1-x)
(OH)2Nanometer sheet is grown on NiCo securely in a manner of erectting2S4Outer layer forms unique, novel 3-D stacks structure, tool
There are very high specific capacitance/area specific capacitance and excellent cyclical stability, it can be directly as the electrode of ultracapacitor.
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